Orthoaminophenyl-n-methylcarbamates

ABSTRACT

N- MONOSUBSTITUTED O-AMINOPHENYLCARBAMATES ARE EFFECTIVE AGAINST PESTS, IN PARTICULAR AGAINST INSECTS, MEMOTODES AND REPRESENTATIVE OF THE ORDER ACARINA. THEN MAY BE USED IN THE FORM OF PESTICIDAL PREPARATIONS.

United States Patent ce 3 781 330 0RTHOAMINOPHENSfL-fi-METHYLCARBAMATESErwin Nikles, Liestal, Switzerland, assignor to Ciba-Geigy AG, Basel,Switzerland No Drawing. Filed Oct. 26, 1970, Ser. No. 84,215 Claimspriority, application Switzerland, Oct. 31, 1969,

1m. 01. Cll7c 125/06 US. Cl. 260-479 C 4 Claims ABSTRACT OF THEDISCLOSURE N-monosubstituted o-aminophenylcarbamates are effectiveagainst pests, in particular against insects, nematodes andrepresentatives of the order Acarina. They may be used in the form ofpesticidal preparations.

This invention relates to new carbamates, their manufacture and theiruse as pesticides.

The present invention provides compounds of the formula in which Rrepresents an alkyl, alkoxyalkyl, alkenyl or alkynyl radical having from3 to 5 carbon atoms, and the acid addition salts thereof with inorganicor organic acids.

Special interest attaches to those compounds in which R represents abranched alkyl, alkoxyalkyl, alkenyl or alkynyl radical having from 3 to5 carbon atoms, and to their corresponding acid addition salts.

Possible groups R are, for example, n-propyl, isopropyl, n-butyl,sec.butyl, tert.butyl, the amyl isomers, B-methoxyisopropyl, allyl,methallyl, crotyl, propargyl, 1-butyn-3-yl, 3-methyl-l-buten-3-yl and3-methyl-1-butyn-3-yl.

The carbamates of the Formula I and their acid addition salts possessvaluable biocidal properties. They are, in particular, active againstall stages of development of sucking, biting and stinging insects,nematodes and representatives of the order Acarina (mites, ticks andspider mites).

Belgian patent specification No. 606,296 has already proposed thecompound of the formula for combating insects, above all aphids.

Belgian patent specification No. 719,776 has proposed compounds offormula R O-C O-lI-Rs (III) 3,781,330 Patented Dec. 25, 1973 and theirsalts especially for combating insects and pests of the order Acarina.Herein, R represents an alkynyl radical having from 3 to =6 carbonatoms, R represents a lower alkyl, alkenyl or alkynyl radical, and R, RR R and R which can be identical or different, are hydrogen or loweralkyl radicals, especially methyl radicals.

It has now been found that the carbamates of the Formula I develop asuperior action in combating insects, Acarina and nematodes as comparedto the compounds of the Formula II or HI.

Using the compounds of Formula I it is possible to combat harmfulinsects, especially those of the orders Corrodentia, Orthoptera,Coleoptera, Thysanoptera, Hymenoptera, Rhynchota, Diptera, Lepidoptera,as well as pests of the order Acarina.

Numerous particularly harmful varieties of insects or varieties ofAcarina are known. Amongst the sucking insects there may for example bementioned: aphids (Aphidae), for example Myzus persicae, Doralis fabae,Rhopalosiphum padi, Macrosiphum pisi, Macrosiphum solanifolii,Cryptomyzus korschelti, Sappaphis mali, Hyalopterus arundinis, Myzuscerasi and also scale insects and mealybugs (Coccina) for exampleAspidiotus hederae, Lecanium hesperidum, Pseudococcus maritimus,varieties of thrips (Thysanoptera), for example Hercinothrips femoralis,bugs, for example Piesma quadrata, Rhodnius prolixus, Dysdercusintermedius, Triatoma infestans or Cimex lectularius, and Cicadas, forexample Eusecelis bilobatus or Nephotettix bipunctatus.

Amongst the biting insects there may for example be mentioned:Lepidoptera such as Plutella maculipennis, Lymantria dispar, Euproctischrysorrhoea, Malocosoma neustria, Mamestra brassicae, Agrotis segetum,Pieris brassicae, Chemz'm'atobia brumata, Tortrix viridana, Prodenialitura, Hyponomenta padella, Ephestia kuhniella and Galleria mellonella,and also storage pests such as Dermestes frz'schiz', T rogodermagranarius, Tribolium castaneum, Sitaphilus granarius and S. zea mais,Stegobium paniceum, Tenebrio molitor, Oryzaephilus surinamensis,Agriotes sp., Blatella germanica, Periplaneta americana, Blattaorientalis, Blaberus gigantus, Blaberus fuscus and Acheta domesticus.

The Diptera mainly comprise the flies (Drosophila melanogaster,Ceratitis capitata, Musca domestica, Lucilia sericata and Calliphora erythrocephala) and the mosquitos (Aedes aegypti, Culex pipiens andAnopheles).

Amongst the representatives of the order Acarina spider mites are to behighlighted as important pests, for example T etranychus telarius, T.althaeae, T. urticae, Paratetranychus pilosus and Panonychus ulmi,blister mites such as Eriophyes ribis, and Tarsonemides, for exampleHemitarsonemus latus and Tarsonemus pallidus. Further, ectoparasitesshould also be mentioned, for example ticks and mites such as Boophilusmicroplus, Dermanyssus gallinae, Ornithonyssus bacoti, Orinthonyssussylviarum, Rhipicephalus bursa, Pneumonyssus caninum, Laelaps nutalli,Acarapis woodi and Psorergat es ovis.

Further, the following genera, which are destroyed by compounds ofFormula I, should be mentioned amongst the nematodes: Heterodera such asH. rostochiensz's and H. schachtii, Meloidogyne such as M. arenaria andM. incognita, Aphelenchus such as A. ritzemab'osi, A. fragariae and A.oryzae, Aphelenchoides, Ditylenchus such as D. dipsaci, Paratylenchus,Rotylenchus, Xiphinema, Rhadopholus, Tylenchulus, Circonemoides,Longidorus, and Trichodorus.

The compounds according to the present invention can be used bythemselves or together with customary pesticidal compounds, especiallyinsecticides, acaricides, nematocides, bactericides, and fungicides.

The present invention also provdies a pesticidal preparation whichcomprises as the active ingredient, at least one carbamate of theformula O-CO-NH-CHa in which R represents an alkyl, alkoxyalkyl, alkenylor alkynyl radical having from 3 to carbon atoms, or an acid additionsalt thereof, together with a suitable carrier and/or further additiveand/or further esticidal compound.

By carriers there are above all understood extenders (solvents or solidor liquid diluents). Additives are intended to encompass othersubstances customary in formulation technology, for example, natural orregenerated mineral substances, suspending agents, emulsifiers, wettingagents, adhesives, thickeners and binders, and also, for example, baitsfor insects, or fertilizers, if for example an improvement of the soilconditions and growth conditions is desired simultaneously withcombating of pests.

Pesticidal compounds which can be added to broaden the spectrum or as adesirable supplement, say in treating a plant culture, can for examplebe taken from the class of the organic phosphorus compounds, thecarbamates, the ureas, the saturated and unsaturated halogen-fattyacids, the triazines, the nitroalkylphenols, the quaternary ammoniumsalts, the sulphamic acids, and the arsenic compounds, borates orchlorates.

The following compounds can, for example, be used as insecticidal,acaricidal and/or nematocidal combination partners:

PHOSPHORIC ACID DERIVATIVES Bis-0,0-diethylphosphoric acid anhydride(TEPP) 0,0,0,0-tetrapropy1dithiopyrophosphate Dimethyl 2,2,2-trichloro-hydroxyethyl phosphonate (Trichlorfon)1,2-dibromo-2,2-dichloroethyldimethylphosphate (Naled)2,2-dichlorovinyldimethylphosphate (Dichlorfos)Z-methoxycarbamyl-1-methylvinyldimethylphosphate (Mevinphos)Dimethyl-l-methyl-Z-(methylcarbamoyl)vinylphosphate cis (Monocrotophos)3-(dimethoxyphosphinyloxy)-N-methyl-N-methoxy-ciscrotonamide3-(dimethoxyphosphinyloxy)-N,N-dimethyl-ciscrotonamide (Dicrotophos)2-chloro-2-diethylcarbamoyl-l-methylvinyldimethylphosphate(Phosphamidon) 0,0-diethyl-O (or S) -2- (ethylthio) -ethylthiophosphate(Demeton) S-ethylthioethyl-0,0-dimethyl-dithiophosphate (Thiometon)0,0-diethyl-S-ethylmercaptomethyldithiophosphate (Phorate)0,0-diethyl-S-2- (ethy1thio)ethyl] dithiophosphate (Disulfoton)0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (Oxydemetonmethyl)0,0-dimethyl-S- 1,2-dicarbethoxyethyl) dithiophosphate (Malathion)(0,0,0,0-tetraethyl-S,S'-methylene-bis- [dithiophosphate] (Ethion) 4O-ethyl-S,S-dipropyldithiophosphate 0,0-dimethyl-S-N-methyl-N-formylcarbamoylmethyl) dithiophosphate (Formotion)0,0dimethy1-S- (N-methylcarbamoylmethyl) dithiophosphate (Dimethat)0,0-dimethyl-S- (N-ethylcarbamoylmethyl) dithiophosphate (Ethoatmethyl)0,0-diethyl-S- (N-isoprop ylcarbamoylmethyl dithiophosphate (Prothoat)S-N-( l-cyanol-methylethyl carbamoylrnethyldiethylthiolphosphate(Cyanthoat) S-(Z-acetamidoethyl)-0,0-dimethyldithiophosphateHexarnethylphosphoric acid triamide (Hempa)0,0-dimethyl-O-pnitrophenylthiophosphate (Parathionmethyl)0,0-diethyl-O-p-nitrophenylthiophosphate (Parathion)O-ethyl-O-p-nitrophenylphenylthiophosphonate (EPN) O, O-dimethyl-O-4-nitro-m-tolyl) thiophosphate (Fenitrothion) 0,0-dimethyl-O-2-chloro-4-nitrophenyl) thiophosphate Dicapthon)0,0-dimethyl-O-p-cyanophenylthiophosphate (Cyanox)O-ethyl-O-p-cyanophenylphenylthiophosphonate0,0-diethyl-A-Z,4-dich1orophenylthiophosphate (Dichrofenthion)O-2,4-dichloropheny1-O-methylisopropylamidothiophoshate O,)-dimethyl-O-2,4,5-trichlorophenylthiophosphate (Ronnel)O-ethyl-O-Z,4,5-trichlorophenylethylthiophosphonate (Trichloronat)0,0-dirnethyl-O-2,S-dichloro-4-bromophenylthiophosphate (Bromophos)0,0-diethyl-O-2,S-dichloro-4-bromophenylthiophosphate (Bromophos-ethyl)0,0-dimethy1-O (2,5-dichloro-4-iodophenyl) -thiophosphate (iodofenphos)4-tert.butyl-2-chlorophenyl-N-methyl-O-methylamidophosphate (Crufomat)Dimethyl-p- (methylthio phenylphosphate 0,0-dimethyl-O- (3-methyl-4-methylmerc aptophenyl) thiophosphate (Fenthion)Isopropylamino-O-ethyl-O-(4-methylmercapto-3- methylphenyl)-phosphate0,0-diethylO-p- (methylsulphinyl phenyl] -thiophosphate (Fensulfothion)0,0-dimethyl-O-p-sulphamidophenylthiophosphate O- [p-(dimethylsulphamido) phenyl] 0-,O-dimethylthiophosphate (Famphur)0,0,0',O'-tetramethyl-0,0'-thiodi-p-phenylenethiophosphateO-(p,(p-chlorophenylazophenyl)0,0-dimethylthiophosphate (Azothoat)O-ethyl-S-phenyl-ethyldithiophosphonateO-ethyl-S-4-chlorophenyl-ethyldithiophosphonateO-isobutyl-S-p-chlorophenyl-ethyldithiophosphonate0,0-dimethyl-S-p-chlorophenylthiophosphate0,0-dimethyl-S-(p-chlorophenylthiomethyl)-dithiophosphate0,0-diethyl-p-chlorophenylmercaptomethyl-dithiophosphate(Carbophenothion) 0,0-diethyl-S-p-chlorophenylthiomethyl-thiophosphate0,0-dimethyl-S- (carb ethoxy-phenylmethyl) dithiophosphate (Phenothoat)0,0-diethyl-S-(carbofluoroethoXy-phenylmethyl)- dithiophosphate0,0-dimethyl-S-(carbisopropoxy-phenylmethyl)-dithiophosphateQO-dimethyl-O-(alpha-methylbenzyl-3-hydroxycrotonyl)phosphate 2-chloro-1- 2,4 dichlorophenyl) vinyl-diethylpho sphate (Chlorfenvinphos)2-chloro-1-(2,4,S-trichlorophenyl)vinyl-dimethylphosphate 7 3-methyl-4-dimethylaminomethyleneiminophenyl-N- methylcarbarnate 3-dimethylarnino-methyleneirninophenyl-N-methylcarbamate1-methylthio-ethylimino-N-methylcarbamate Me thoxymylZ-rnethylcarbarnoyloxyimino-1,3-dithiolaneS-methyl-Z-methylcarbamoyloxyimino-1, 3 -oxathilane 2( l-methoxy-Z-propoxy) phenyl-N-methylcarbamate 2( 1-butin-3-yl-oxyphenyl-N-methylcarbamate 3 -methyl-4-dimethylamino-methylrnercapto-methyleneimino phenyl-N-methylcarbamate1,3-bis (carbamoylthio) -2- (N,N-dimethylamino -pr0pane hydro chloride 5,5 -dimethylhy droresorcinoldimethylcarbamate 2- propargylethyl amino]-phenyl-N-methylcarbamate 2- [propargylrnethylamino]-phenyl-N-methylcarb am ate 2- [dipropargylamino] -phenyl-N-methylcarbamate 3 -methyl-4- [diprop argylamino] -phenyl-N-methy1- carbamate 3 ,5-dimethyl-4- [dipropargylamino] -phenyl-N-methy1- carbamate 2-[allyl-isopropylamino] -phenyl-N-methylc arbamate and 3[allyl-isopropylamino] -phenyl-N-methylcarbamate.

CHLORINATED HY DROCARB ONS y-Hexachlorocyclohexane [Gammexane; Lindane;'y

HCH] 1,2,4,5,6,7,8,8-octachloro-3a,4,7,7a'-tetrahydro-4,7-

methyleneindane [Chlordan]1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-

methyleneindane [Heptachlor]1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-heXahydro-endo-1,4-ex0-5,S-dimethanonaphthalene [Aldrin]1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4u,5,6,7,8,8u,9-

octahydro-exo-1,4-endo-5,8-dimethanonaphthalene [Dieldrin] Endrin6,7,8,9,10,IO-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9- methano-2,3,4benzo[e]-dioxa-thiepene-3-oxide [Endosulfan] Chlorinated camphor[Toxaphen] Decachlorooctahydro-1,3,4-metheno-2H-cyclobuta[ed]pentalen-Z-one Dodecachlorooctahydro-1,3,4-metheno-lH-cyclobuta-[cd]pentalene [Mirex]Ethyl-1',1oc,3,30:,4,5,5oz,50:,6-(166aChIOIOOCiQhYdI'O-Z-hydroxy-1,3,4-metheno-1H-cyclobuta[cd]pentalene- 2-laevulinate Bis(pentachloro-ZA-cyclopentadienel-yl) Dinoctone-o1,1,1-trich1oro-2,2-bis(p-chlorophenyl)ethane [DDT]Dichlorodiphenyl-dichlorethane [TDE]Di(p-chlorophenyl)-trichloromethylcarbinol [Dicofol]Ethyl-4,4'-dichlorophenylglycollate [Chlorobenzylate]Ethyl-4,4-dibromobenzy1ate [Bromobenzylate]Isopr0pyl-4,4-dichlorobenzylate 1,1,1-trich1oro-2,2 bis(p-methoxyphenyl)ethane [Methoxychlor] Diethyl-diphenyl-dichlorethane vDecachloropentacyclo(3,3,2,0 ,0 ,0 )decan-4-one [Chlordecon]NITROPHENOLS AND DERIVATIVES 4,6-dinitro-6-methylphenol Na salt[Dinitrocresol] Dim'trobutylphenol-Z,2',2"-triethanolamine salt2-cyclohexyl-4,6-dinitropheno1 [Dinex] 2-1-methy1heptyl)-4,6-dinitrophenyl-crotonate [Dinocap] 2sec.-butyl-4,6-dinitropheny1-3-methyl-butenoate [Binapacryl] 2sec.-butyl-4,6-dinitrophenyl-cyclopropionate and 2 sec.-butyl-4,6dinitrophenyl-isopropyl-carbonate [Dinobuton] 8 VARIOUS SUBSTANCESSabadilla Rotenone Cevadine Veratridine Ryania Pyrethrin3-allyl-2-methyl-4-oxo-2-cyclopenten-l-yl-chrysanthemumate (Allethrn)6-chloropiperonyl-chrysanthemumate (Barthrin)2,4-dimethylbenzyl-chrysanthemumate (Dimethrin)2,3,4,5-tetrahydrophthalimidornethyl-chrysanthemumate (5-benzyl-3-furyl)-methyl-2,2-dimethyl-3- (Z-methylpropanyl) cyclopropanecarboxylateNicotine Bacillus thuringienszs' Berliner DicyclohexylcarbodiimideDiphenyldiimide [azobenzene (sic)] 4-chlorobenzyl-4-chlorophenylsulphide[Chlorbensid] Creosote oil 6-methyl-2-oxo- 1 ,3 -dithiolo- [4,5 -b]-quinoxaline [Quinomethionat] (I) -3- (Z-furfuryl)-2-methyl-4-oxocyclopent-2-enyl (I) (cis-i-trans) chrysanthemum-monocarboxylate [Furethrin] 2-pivaloy1-indane-1,3-dione[Pindon] Z-fiuorethyl (4-bispheny1 acetate Z-fluOro-N-methyI-Nl-naphthyl) -acetamide Penthachlorophenol and salts2,2,2-trichloro-N-(pentachlorophenyl)-acetimidoyl chloride N'-4-chloro-2-methylphenyl) -N,Ndimethylformamidine (Chlorphenamidine)4-chlorobenzyl-4-fluorophenyl-sulphide (Fluorobenside)5,6-dichloro-1-phenoxycarbanyI-Z-trifluoromethylbenzimidazole(Fenozaflor) Tricyclohexyl-stannic hydroxide 2-thiocyanatoethyl-lauricacid ester ,B-Butoxy-B'-thiocyanatodiethyl-etherIsobornyl-thiocyanatoacetate p-Chlorophenyl-p-chlorobenzenesulphonate(Ovex) 2,4-dichlorophenyl-benzenesulphonatep-chlorophenyl-benzenesulphonate (Fenson)p-chlorophenyl-2,4,S-trichlorophenylsulphone (Tetradifon)p-ch1orophenyl-2,4,S-trichlorophenylsulphide (Tetrasul) Methyl bromidep-chlorophenyl-phenylsulphone p-chlorobenzyl-p-chlorophenylsulphide(Chlorobenside) 4-chlorophenyl-2,4,S-trichlorophenylazosulphide2(p-tert.-butylphenoxy-1-methylethyl-2-chlorethylsulphite 2(p-tert.-butylphenoxy) cyclohexyl-Z-propinyl-sulphite4,4-dichloro-N-methylbenzenesulphonanilideN-(Z-fiuoro-1,1,2,2-tetrachlorethylthio)-methanesulphonanilide2-thio-1,3-dithio1o-(4,5,6)quinoxaline (Thioquinox)Chloromethyl-p-chlorophenylsulphone lauseto (sic!) new)l,3,6,8-tetranitrocarba'zole and Prop-2-inyl- 4-t-butylphenoxy)-cyc1ohexylsulphite (Propargil) The action of the carbamates accordingto the invention can be increased yet further by synergistic agents.Suitable substances for this purpose are for example Sesamin, Sesamex,piperonyl-cyclonene, piperonyl-butoxide, piperonalbis(2-(2-butoxyethoxy)ethyl)acetate, sulphoxides, propyl isome (sic), N-(Z-ethylhexyD-S-norbornene-2,B-dicarboxamide, octachlorodipropyl-ether,2- nitrophenyl propargylether, 4-chloro-2-nitrophenyl-propargyl-etherand 2,4,5-trichlorophenyl-propargyl-ether.

Pesticides which contain compounds of Formula I as active substances,can be used in the most diverse way and in various forms, for example inthe form of solutions,

sprays, dusting powders, scattering agents, granules, spraying powders,emulsions, dispersions and suspensions, and also so-called fly dishes orfly strips which are impregnated with a solution of the activesubstances.

To manufacture directly sprayable solutions of the compounds of FormulaI, it is for example possible to use mineral oil fractions of high tomedium boiling range, such as diesel oil or kerosene, coal tar oil andoils of vegetable or animal origin, as well as hydrocarbons, such asalkylated naphthalenes and tetrahydronaphthalene, optionally with theuse of xylene mixtures, cyclohexanols, ketones and also chlorinatedhydrocarbons, such as trichloroethane, trichloroethylene ortrichlorobenzenes and tetrachlorobenzenes. Organic solvents of boilingpoint above 100 C. are advantageously used.

Aqueous application forms are particularly appropriately prepared fromemulsion concentrates, pastes or wettable spraying powders, by addingwater. Possible dispersing agents are non-ionic products, for examplecondensation products of aliphatic alcohols, amines or carboxylic acidshaving a long-chain hydrocarbon radical of about to carbon atoms withethylene oxide, such as the condensation products of octadecyl alcoholand to mols of ethylene oxide or that of technical oleylamine and 15mols of ethylene oxide or that of dodecylmercaptan and 12 mols ofethylene oxide. Amongst the anionic emulsifiers which can be employed,there may be mentioned: the sodium salt of dodecyl alcohol sulphuricacid ester, the sodium salt of dodecylbenzenesulphonic acid, thepotassium salt or triethanolamine salt of oleic acid or of abietic acidor of mixtures of these acids, or the sodium salt of apetroleumsulphonic acid. Possible cationic dispersing agents arequaternary ammonium compounds, such as cetylpyridinium bromide ordihydroxyethylbenzyldodecylammonium chloride.

To manufacture dusting and scattering agents, it is possible to employtalc, kaolin, bentonite, calcium carbonate and calcium phosphate, butalso charcoal, cork powder, woodflour and other materials of vegetableorigin as solid carriers. The use of the preparations in a granular formis also very appropriate, for example for combating soil insects, soilfungi or pests in rice cultures.

Granules can be manufactured very simply by dissolving an activesubstance of Formula I in an organic solvent, applying the solution thusobtained to a granular mineral, for example attapulgite, SiOgranicalcium, bentonite and the like, and then again evaporating theorganic solvent.

It is also possible to use polymer granules. They can be manufactured bymixing the active substances of Formula I with polymerisable compounds(urea/formaldehyde, dicyandiamide/ formaldehyde, melamine/ formaldehydeor others), after which a polymerisation is carried out under mildconditions, which leaves the active substances unaffected, andgranulation is carried out whilst the gel formation is still proceeding.It is more advantageous to impregnate finished, porous polymer granules(urea/formaldehyde, polyacrylnitrile, polyesters and others) having aparticular surface area and a favorable predeterminableadsorption/desorption ratio, with the active substances, for example inthe form of their solutions (in a low-boiling solvent) and to remove thesolvent. Such polymer granules, in the form of microgranules with bulkdensities of preferably 300 g./litre to 600 g./litre, can also beapplied with the aid of atomizers. Atomizing over extended areas ofcropplant cultures can be carried out with the aid of aircraft.

Granules are also obtainable by compacting the carrier with the activesubstances and additives, and subsequent comminution.

The various application forms can, in the usual manner, be provided withthe addition of substances which improve the distribution, the adhesion,the rain resistance or the penetrating capacity; as such substancesthere may be mentioned: fatty acids, resins, glues, caseins oralginates. When processing the active substances of Formula l to giveready-to-apply agents, an important factor v in the choice of theauxiliary substances will be whether the carbamates are employed in thefree form or in the form of a salt.

As a rule, the agents according to the invention contain 0.005 to aboutof an active substance of Formula I. In individual cases, technicallypure active substance can also be employed for combating pests, usingapplication equipment which provides extremely fine distribution. Thepresent invention also provides a process for the manufacture of thecarbamates of the Formula I, wherein the carbamate of the formula NHz isN-monoalkylated with a reactive ester of an alcohol of the formula RO H,R having the meaning specified above.

As reactive esters of the alcohol ROH, the hydrogen halide acid esters,for example, the chlorides, bromides or iodides are advantageously used;it is, however, also possible to use sulphonic acid esters, for example,the mesylates or tosylates, with equal success for the N- alkylation.

In a similar manner, it is also possible to N-monoalkylate a carbonateof the formula NH: NH:

and subsequently to convert the product into carbamates of Formula I bymeans of methylamine.

The compounds of the Formula I can also be manufactured from thecompounds of the Formulae IV or V, or the nitro compounds on which theyare based, by reductive monoalkylation with lower aliphatic carbonylcompounds (for example, propionaldehyde, butyraldehyde, acetone ormethyl ethyl ketone), splitting with methylamine again being necessaryin the case of carbonates of the Formula V. Depending on the specificproperties of the compounds, it may be advantageous to isolate thealdimines or ketimines which occur as intermediates. Catalyticallyactivated hydrogen is preferably used as the reducing agent.

The carbamates thus obtained can, if desired, be converted into theiracid addition salts with inorganic or organic acids. Depending on thesolubility of the salts produced, the salt formation can be carried outin a solvent free of hydroxyl groups or in a solvent containing hydroxylgroups, such as methanol, ethanol, isopropanol, acetone or methyl ethylketone. Hydrohalic acids, such as hydrochloric acid, HBr or HI are, forexample, suitable for the salt formation, as are phosphoric acid,sulphuric acid, nitric acid, perchloric acid, iodic acid, sulphamicacid, oxalic acid, maleic acid, citric acid, tartaric acid, succinnicacid, glycollic acid, ethionic acid, phthalic acid, methanesulphonicacid, benzenesulphoni'c acid, p-toluenesulphom'c acid andtrichloroacetic acid.

In general, the stability of the carbamate is increased by saltformation. Acid salts, for example, the acid sulphate of2-isopropylamine-phenyl-N-methylcarbamate, are distinguished byparticular stability.

The following examples illustrate the invention, the parts being byweight.

EXAMPLE 1 2-isopropylamino-phenyl-N-methylcarbamate (Compound No. 1)

A mixture of 830 parts of Z-aminophenyl-N-methyl- 'carbamate, 1300 partsof isopropyl bromide, 800 parts by volume of dioxane and 100 parts byvolume of dimethylformamide is stirred for 2 days at 60-65 C. andsubsequently evaporated in a waterpump vacuum. The residue is treatedwith 2000 parts by volume of ether and an equal quantity of saturatedsodium bicarbonate solution. The ether phase is separated off, washedwith water, dried over anhydrous sodium sulphate and evaporated. Theresidue mainly consists of 2-isopropylamino-phenyl-N- methylcarbamate.Chromatography on silica gel (elution with toluene) yields the pureproduct. Melting point 7072. C.

The starting product, 2-aminophenyl-N-methylcarbamate, can bemanufactured as follows:

A solution of 196 parts of 2-nitrophenyl-N-methylcarbamate in 700 partsby volume of glacial acetic acid is shaken in a hydrogen atmosphere, inthe presence of 2.4 parts of 10 percent strength palladium on charcoal.When hydrogen absorption has ceased, the catalyst is filtered off andthe filtrate is evaporated in vacuo. The residue is triturated withwater, filtered, dried and crystallized from chloroform. Melting pointl26128 C.

EXAMPLE 2 2-propargyla'minophenyl-N-methylcarbamate (Compound No. 2)

70 parts of 2-aminophenyl-N-methylcarbamate are dissolved in 100 partsby volume of approx. 10 percent strength aqueous hydrochloric acid. 55parts of propargyl bromide are added dropwise to this solution, whilststirring in a nitrogen atmosphere. The pH value of the solution is keptat 4-5 by simultaneously adding 30 percent strength sodium hydroxidesolution. After completion of the reaction, the mixture is renderedalkaline and extracted with toluene. The toluene solution is dried,filtered and evaporated in vacuo. The residue is crystallized fromtoluene. Melting point 102-l04 C.

EXAMPLE 3 2-( 1', 1'-dimethyl-2'-propinyl-amino)-phenyl-Nmethylcarbamate (Compound No. 3)

83 parts of 2-aminophenyl-N-methylcarbamate are suspended in 300 partsof water in a nitrogen atmosphere. Thereafter parts of copper-I chlorideand, as are 62 parts of 3-chloro-3-methyl-l-butine are addedthe latterdropwise-whilst stirring. The mixture is kept at pH 4-5 by continuousaddition of 5 percent strength sodium hydroxide solution and at approx.20 C. by cooling. After completion of addition of the3-chloro-3-methyl-1- butine the mixture is stirred for a further /2 hourat 20 C., subsequently treated with 300 parts by volume of ether,brought to pH=7 with sodium bicarbonate solution and filtered throughCelite. The organic phase is separated off, washed with water, driedover anhydrous sodium sulphate and evaporated. The residue iscrystallized from cyclohexane. Melting point 89--92 C.

EXAMPLE 4 2-( 1,1'-dimethyl-allyl-amino)phenyl-N-methylcarbamate(Compound N0. 4)

A solution of 70 parts of 2-(l,l'-dimethyl-'-p1-opinylamino)phenyl-N-methylcarbamate in 200 parts by volume ofpyridine is mixed with 3.5 parts of a 10 percent strength palladiumcatalyst (on calcium carbonate) and shaken in a hydrogen atmosphereuntil the theoretical amount of hydrogen has been taken up. The catalystis filtered off and the solution is evaporated in vacuo. The residue isdissolved in ether, washed with dilute sodium hydroxide solution underice-cold conditions, and chromatographed on silica gel. The product iscrystallized from hexane. Melting point 66 C.

By hydrogenation with palladium on charcoal in dioxane,2-(l,l-dimethyl-propyl-amino)-pheny1-N-methylcarbamate is obtained fromthe above product. Melting point 57-62 C. (Compound No. 5).

EXAMPLE 5 2-( l-methoxy-2'-propy1-amino) phenyl-N-methylcarbamate(Compound No. 6)

parts of l-methoxy-2-propy1-tosylate are added dropwise at 50 C. to amixture of 83 parts of Z-aminophenyl-N-methylcarbamate, 15 parts ofpotassium iodide and 48 parts of dry pyridine. The mixture is kept for afurther 14 hours at 60 C. and is then cooled and poured onto 1000 partsof ice water. The oily product is obtained by extraction with ether andevaporation of the solvent, and is purified by chromatography on silicagel (elution with toluene).

NMR spectrum: (i=6 cps.), 3H,

a-values (CDCl /TMS). 1.22, d

approx. 5.3, b, 1H, (CO N HCH 6.5-7.3, m, 4H (aromat. H).

The following can be manufactured in a similar manner:

EXAMPLE 6 (a) Dusting agents Equal parts of an active substanceaccording to the invention and of precipitated silica are finely ground.Dusting agents preferably containing l6% of active substance can bemanufactured therefrom by mixing with kaolin or talc.

(b) Spraying powders To manufacture a spraying powder the followingcomponents, for example, are mixed and finely ground:

50 parts of active substance according to the present invention,

20 parts of highly adsorbent silica,

25 parts of Bolus alba (kaolin),

1.5 parts of sodium 1-benzyl-2-stearyl-benzimidazole-6,

3'-disulphonate and 3.5 parts of a reaction product ofp-tert.octylphenol and ethylene oxide.

(0) Emulsion concentrate Easily soluble active substances can also beformulated as an emulsion concentrate in accordance with the followinginstruction:

20 parts of active substance 70 parts of xylene and 10 parts of amixture of a reaction product of an alkyl phenol with ethylene oxide andcalcium dodecylben' zenesulphonate are mixed. 0n dilution with water tothe desired concentration, a sprayable emulsion is produced.

13 (d) Granules parts of an active substance according to the inventionand 5 parts of talc are mixed and finely ground. On mixing in a further90 parts of tale, a 5% strength dusting powder is obtained as thestarting mixture for an active substance dilution series for testingagainst storage pests on filter paper in glass dishes. 2 g. of thismixture per glass dish correspond to 100 mg. of active substance/m9.

Further 1:1 dilutions of the 5% strength dusting powder yield 2.5%strength, 1.25% strength, 0.62% strength, 0.31% strength, 0.16% strengthand 0.08% strength mixtures which correspond to an amount of activesubstance of 50, 25, 12.5, 6.2, 3.1 and 1.5 mg. of active substance/m if2 g. of the particular dust formulation are used per glass dish.

Evaluation after 24 hours showed that the following minimumconcentrations were necessary, for complete destruction of theparticular pests:

EXAMPLE 8 Action against Aphis fabae Young Vicia faba plants about 6 cm.high were infested with parts of plants attacked by A phis' fabae. After5 days, the starting conditions for the active substance test existed asa result of further growth of the plants and correspondingly greatincrease in the aphids. The attacked plant was sprayed with an emulsionof the active substance to be tested from all sides (contact action) oronly from above, in the direction of the axis of the shoot (penetrationaction). In the latter case, the test insects on the undersides of theleaves are not struck by the spray jet. If 100% mortaliity was alreadyfound after 2 days, the plant was re-infested.

In comparison with the compound N-CHz-CECH (Compound A) known fromBelgian patent specification 719,776 and compound N-CH; (Compound B)known from Belgian patent specification 606,296, the followingmortalities expressed as a percentage, were 14 achieved with thecompounds according to the present invention:

Concen- Contact action Penetra- Compound tration tion number (p.p.m.) 2days 5 days 2 days The compounds according to the present inventionadditionally, and in contrast to the comparison Compounds A and B,possess a systemic action, that is to say they are absorbed by the plantand transported with the sap flow.

EXAMPLE 9 Contact action on Ceratitis capitata 1 half of a Petri dishwas in each case treated with 1 ml. of an acetone solution containing1000, 100, 10, 5, 2.5 and 1.25 p.p.m. of the active substance to betested. After evaporation of the solvent, 10 sub-cooled Mediterraneanfruit flies were introduced into the prepared Petri dishes and the lidhalves were placed in position. After increasing time intervals, thedestruction was examined at the various concentrations. The followingpercentage mortality was achieved after 2 hours:

Compound number Concentration (p.p.m. 1 3 6 9 1O 12 EXAMPLE 10 phane bagwhich was subsequently fixed over the treated plant by means of a rubberband. After 5 days the efiect of the treatment was determined bycounting the live and dead animals and by calculating the percentagemortality.

Compound number Concentration (p.p.m.) 1 2 6 7 10 12 (b) The test wasOrgyia gonostigma in the L-3 stage was carried out analogously, withyoung mallows (Malva silvestris) as the host plant. 5 larvae were usedfor each test. Evaluation took place after 2 and 5 days. If completemortality had already occurred after 2 days, the plant was re-infested.Cln this way, a possible ageing of the active substance coating is alsotaken into account in the evalua- Action against assassin bugs (Rhoaniusprolixus). Solutions of the active substance, in acetone, are applied inPetri dishes of 11 cm. diameter in such a way that concentrations of 1mg., 0.1 mg., 0.01 mg. and 0.001 mg. per dish are provided. (1 mg. perdish corresponds to 1 g. per 9.4 mfi.) After one hours drying of theprepared dishes, 20 bugs in the L-3 stage are exposed to the activesubstance coating for 24 hours. The action is tested after 24 hours.

A single repeat was run with a new dilution series. Total mortalitieswere achieved with the following minimum concentrations of theparticular active substances:

Minimum concen- Compound No.: tration (mg/dish) 16 What is claimed is:

1. A carbamate of the formula in which R represents an alkyl,:alkoxyalkyl, alkenyl or al kynyl radical having from 3 to 5 carbonatoms, or an acid addition salt.

2. A carbamate according to claim 1, in which R represents a branchedalkyl, alkoxyalkyl, alkenyl or alkyn'yl radical having from 3 to 5carbon atoms, or an acid addition salt.

3. The carbamate of the formula or an. acid addition salt according toclaim 2.

4. The carbamate of the formula or an acid addition salt according toclaim 2.

References Cited UNITED STATES PATENTS 3,522,292 7/1970 Nikles 260-4793,160,554 12/1964 'Heiss et a1. 260--479 OTHER REFERENCES Warner et al.:Synthetic Organic Chem, Sons, New York (1955), p. 667.

JAMES A. PATTEN, Primary Examiner US. Cl. X.R.

Wiley and

